Title:
Oxime ethers and fungicides containing these compounds
United States Patent RE33989


Abstract:
Oxime ethers of the formula ##STR1## where R1 and R2 are hydrogen or alkyl, X(m=1 to 5) is halogen, cyano, trifluoromethyl, nitro, allyl, alkoxy, unsubstituted or substituted phenyl, unsubstituted or substituted phenoxy, unsubstituted or substituted benzyloxy or hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethynylene or oxygen, and fungicides containing these compounds.



Inventors:
Wenderoth, Bernd (Lampertheim, DE)
Anke, Timm (Kaiserslautern, DE)
Rentzes, Costi (Heidelberg, DE)
Ammermann, Eberhard (Ludwigshafen, DE)
Pommer, Ernst-heinrich (Limburgerhof, DE)
Steglich, Wolfgang (Bonn-Roettgen, DE)
Application Number:
07/540817
Publication Date:
07/07/1992
Filing Date:
06/11/1990
Assignee:
BASF Aktiengesellschaft (Ludwigshafen, DE)
Primary Class:
Other Classes:
514/539, 514/567, 558/412, 558/414, 560/21, 560/35, 562/435, 562/440
International Classes:
A01N37/50; C07C251/48; C07C255/61; (IPC1-7): A61K31/275
Field of Search:
515/552, 515/539, 515/567, 558/412, 558/414, 560/21, 560/35, 562/435, 562/440
View Patent Images:



Foreign References:
GB1404221A1975-08-28562/440
Primary Examiner:
REAMER, JAMES H
Attorney, Agent or Firm:
OBLON, SPIVAK, MCCLELLAND, (MAIER & NEUSTADT 1755 JEFF. DAVIS HWY., 4TH FL, ARLINGTON, VA, 22202, US)
Parent Case Data:

This application is a continuation of application Ser. No. 069,224, filed on July 2, 1987, now abandoned.

Claims:
We claim:

1. An oxime ether of the formula I ##STR19## where R1 is hydrogen or alkyl of 1 to 5 carbon atoms, R2 is methyl, the radicals X (m=1 to 5) are identical or different substituents from the group consisting of halogen, cyano, trifluoromethyl, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, phenyl, unsubstituted or halo or alkyl substituted phenoxy, unsubstituted or halo or alkyl substituted benzyloxy, and hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene or oxygen.

2. An oxime ether of the formula I as set forth in claim 1, where X is hydrogen, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro-6-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-bromo, 3-bromo, 4-bromo, 2,4-dichloro, 2,6-dichloro, 3,5-dichloro, 2,4,6-trichloro, 2-chloro-4-methyl, 2-methyl-4-chloro, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-isopropyl, 4-tert.-butyl, 2,4-dimethyl, 2,6-dimethyl, 2,4,6-trimethyl, 2-methoxy-4-methyl, 4-methoxy-2-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 4-ethoxy, 4-isopropoxy, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-cyano, 4-cyano, 3-nitro, 4-nitro, 4-phenyl, 4-benzyloxy, 4-phenoxy, halophenoxy, 4-(2-chloro)-phenoxy, 4-(2,4-dichloro)-phenoxy, C1 -C4 -alkylphenoxy, 4-(2-methyl-phenoxy, 3-benzyloxy, halobenzyloxy, 3-(2-chloro)-benzyloxy, 3-(2,4-dichloro)-benzyloxy, 3-(2-fluoro)-benzyloxy, 3-(4-bromo)-benzyloxy-, C1 -C4 -alkylbenzyloxy, 3-(2-methyl)-benzyloxy, 3-phenoxy, 3-(2-chloro)-phenoxy, 3-(2,4-dichloro)-phenoxy, 3-(2-fluoro)-phenoxy, 3-(4-bromo)-phenoxy or 3-(2-methyl)-phenoxy, R1 is hydrogen, methyl, ethyl or isopropyl.

3. A fungicidal agent containing an oxime ether of the formula I ##STR20## wherein R1 is hydrogen or alkyl of 1 to 5 carbon atoms, R2 is methyl, the radicals X (m=1 to 5) are identical or different substituents from the group consisting of halogen, cyano, trifluoromethyl, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, phenyl, unsubstituted or halo or alkyl substituted phenoxy, unsubstituted or halo or alkyl substituted benzyloxy, and hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene or oxygen, and inert carriers.

4. A process for combating fungi, wherein an oxime ether of the formula I ##STR21## where R1 and R2 are identical or different and are each hydrogen or alkyl of 1 to 5 carbon atoms, the radicals X (m=1 to 5) are identical or different substituents from the group consisting of halogen, cyano, trifluoromethyl, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, phenyl, unsubstituted or halo or alkyl substituted phenoxy, unsubstituted or halo or alkyl substituted benzyloxy, and hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene or oxygen, is allowed to act on the fungi, or the areas, plants, materials or seed threatened by fungus attack.

5. 2-Benzyloxyphenyl-glyoxylic acid methyl ester O-methyloxime.

6. 2-Phenyloxymethylenephenyl-glyoxylic acid methyl ester O-methyloxime.

7. The oxime ether according to claim 1, wherein Y is methyleneoxy.

8. The oxime ether according to claim 1, wherein Y is oxymethylene.

9. The oxime ether according to claim 1, wherein Y is ethylene.

10. The oxime ether according to claim 1, wherein Y is ethenylene.

11. The oxime ether according to claim 1, wherein Y is ethynylene.

12. The oxime ether according to claim 1, wherein Y is oxygen.

13. The oxime ether according to claim 2, wherein Y is --CH2 O--.

14. The oxime ether according to claim 2, wherein Y is --OCH2 --.

15. The oxime ether according to claim 2, wherein Y is --CH2 CH2 --.

16. The oxime ether according to claim 2, wherein Y is --CHCH--.

17. The oxime ether according to claim 2, wherein Y is --CC--.

18. The oxime ether according to claim 2, wherein Y is --O--.

19. The fungicidal agent of claim 3, wherein in the oxime ether Y is methyleneoxy.

20. The fungicidal agent of claim 3, wherein in the oxime ether Y is oxymethylene.

21. The fungicidal agent of claim 3, wherein in the oxime ether Y is ethylene.

22. The fungicidal agent of claim 3, wherein in the oxime ether Y is ethenylene.

23. The fungicidal agent of claim 3, wherein in the oxime ether Y is ethynylene.

24. The fungicidal agent of claim 3, wherein in the oxime ether Y is oxygen.

25. The process according to claim 4, wherein in the oxime ether Y is methyleneoxy.

26. The process according to claim 4, wherein in the oxime ether Y is oxymethylene.

27. The process according to claim 4, wherein in the oxime ether Y is ethylene.

28. The process according to claim 4, wherein in the oxime ether Y is ethenylene.

29. The process according to claim 4, wherein in the oxime ether Y is ethynylene.

30. The process according to claim 4, wherein in the oxime ether Y is oxygen.

31. The oxime ether of claim 1, wherein R1 is methyl, Y is oxymethylene, m=1 or 2, when m=2, X is in the 2 and 4 positions and each X is selected from halogen or methyl, and wherein m=1, X is 2-halogen, 4-halogen, 2-methyl, 4-methyl or 2-methoxy.


32. The oxime ether of claim 31, wherein halogen is selected from the group consisting of fluorine and chlorine.


Description:

The present invention relates to novel oxime ether derivatives, their preparation and their use as fungicides.

It is known that N-tridecyl-2,6-dimethylmorpholine and its salts, for example the acetate, can be used as fungicides (DE-1 164 152 and 1 173 722). However, their action is inadequate in some cases. It is also known that acrylic acid derivatives, e.g. methyl 2-(4-[p-chlorostyryl]-phenyl)-3-methoxyacrylate, can be used as fungicides (European Pat. No. 178,826). However, their action is unsatisfactory.

We have found that novel oxime ether derivatives of the formula I ##STR2## where R1 and R2 are identical or different and are each hydrogen or alkyl of 1 to 5 carbon atoms, the radicals X (m=1 to 5) are identical or different substituents from the group consisting of halogen, cyano, trifluoromethyl, nitro, C1 -C4 -alkyl, C1 -C4 -alkoxy, unsubstituted or substituted phenyl, unsubstituted or substituted phenoxy, unsubstituted or substituted benzyloxy and hydrogen, and Y is methyleneoxy, oxymethylene, ethylene, ethenylene, ethynylene or oxygen, not only possess very high fungitoxic activity but also are very well tolerated by plants.

Because of the CN double bond, the novel compounds of the formula I are obtained in their preparation in the form of E/Z isomer mixtures, which can be separated into the individual components in a conventional manner, for example by crystallization or chromatography. The invention relates both to the individual isomeric compounds and to mixtures of these.

R1 is preferably hydrogen or C1 -C3 -alkyl, such as methyl, ethyl or isopropyl, and R2 is preferably hydrogen or C1 -C5 -alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl or neopentyl.

X is preferably hydrogen, 2-fluoro, 3-fluoro, 4-fluoro, 2-chloro-6-fluoro, 2-chloro, 3-chloro, 4-chloro, 2-bromo, 3-bromo, 4-bromo, 2,4-dichloro, 2,6-dichloro, 3,5-dichloro, 2,4,6-trichloro, 2-chloro-4-methyl, 2-methyl-4-chloro, 2-methyl, 3-methyl, 4-methyl, 4-ethyl, 4-isopropyl, 4-tert-butyl, 2,4-dimethyl, 2,6-dimethyl, 2,4,6-trimethyl, 2-methoxy-4-methyl, 4-methoxy-2-methyl, 2-methoxy, 3-methoxy, 4-methoxy, 4-ethoxy, 4-isopropoxy, 2-trifluoromethyl, 3-trifluoromethyl, 4-trifluoromethyl, 2-cyano, 4-cyano, 3-nitro, 4-nitro, 4-phenyl, 4-benzyloxy, 4-phenoxy, halophenoxy, 4(2-chlorophenoxy), 4-(2,4-dichlorophenoxy), C1 -C4 -alkylphenoxy, 4-(2-methylphenoxy), 3-benzyloxy, halobenzyloxy, 3-(2-chlorobenzyloxy), 3-(2,4-dichlorobenzyloxy), 3-(2-fluorobenzyloxy), 3-(4-bromobenzyloxy), C1 -C4 -alkylbenzyloxy, 3-(2-methylbenzyloxy), 3 -phenoxy, 3-(2-chlorophenoxy), 3-(2,4-dichlorophenoxy), 3-(2-fluorophenoxy), 3-(4-bromophenoxy) or 3-(2-methylphenoxy), and Y is preferably a --CH2 O--, --OCH2 --, --CH2 --CH2 --, --CHCH-- or --CC-- group or O.

The novel compounds can be prepared by reacting an α-ketocarboxylate of the formula II ##STR3## where Xm, Y and R1 have the above meanings, (a) with an O-substituted hydroxylamine of the general formula III H2 N--O--R2 (III)

where R2 has the above meanings, or

(b) with hydroxylamine to give the corresponding oxime, and then reacting the product with a halogen derivative of the formula IV R2 --X (IV)

wherein R2 has the above meanings and X is halogen (F, Cl, Br or I), or with a dialkyl sulfate.

The α-ketocarboxylates of the formula II can be prepared, for example, by reacting the corresponding aromatic Grignard compounds with imidazolides of the formula V ##STR4## where R1 has the above meanings (J. S. Nimitz and H. S. Mosher, J. Org. Chem. 46 (1981), 211-213.

The Example which follows illustrates the preparation of the novel compounds of the formula I.

(a) Preparation of methyl 2-(benzyloxy)-phenylglyoxylate

0.1 mole of a Grignard compound prepared from 1-benzyloxy-2-bromobenzene and magnesium turnings in tetrahydrofuran is slowly added dropwise 14.6 g (95 millimoles) of methyloxalylimidazole in tetrahydrofuran under nitrogen at -50° C. The mixture is allowed to come slowly to room temperature (20° C.) over a period of 4 hours. It is poured onto ice water and extracted several times each ether. The combined ether phases are washed neutral and dried. After the solvent has been evaporated off, the product is brought to crystallization with n-pentane to give 16 g (62%) of colorless crystals of the abovementioned compound.

1 H-NMR(CDCL3): δ=3.35 (s,3H), 5.07 (s,2H), 7.05 (m,2H), 7.40(m,5H), 7.55 (m,1H), 7.90 (m,1H).

(b) Preparation of (Z)-(2-benzyloxyphenyl)-glyoxylic acid methyl ester O-methyloxime (compound no. 83) 15.5 g (57 millimoles) of methyl 2-(benzyloxy)phenylglyoxylate in 160 ml of methanol are initially taken, and 11.5 g of sodium carbonate and 9.45 g (114 millimoles) of O-methylhydroxylamine hydrochloride are added. The stirred mixture is refluxed for 24 hours. 100 ml of water are added, after which the mixture is extracted several times with ethyl acetate and the ethyl acetate solution is dried with Na2 SO4 and then evaporated down.

11 g (65%) of the abovementioned compound are obtained in the form of an isomer mixture. Mixing with n-pentane gives the pure (Z)-isomer as white crystals of melting point 120°-132° C.

13 C-NMR (CDCL3):δ=52.50, 62.92, 70.93, 112.60, 120.49, 121.33, 128.19, 128.52 (2c) 129.04 (3C), 131.70, 135.92, 148.44, 156.50, 163.84.

The compounds listed in the Table below can be prepared by appropriately modifying the above data.

__________________________________________________________________________
##STR5## (I) Comp. No. Xm Y R1 R2 Isomer Mp(°C.) IR(cm-1)
__________________________________________________________________________

1 H CH2CH2
CH3
CH3
2 2-F CH2CH2
CH3
CH3
3 3-F CH2CH2
CH3
CH3
4 4-F CH2CH2
CH3
CH3
5 2-Cl, 6-F CH2CH2
CH3
CH3
6 2-Cl CH2CH2
CH3
CH3
7 3-Cl CH2CH2
CH3
CH3
8 4-Cl CH2CH2
CH3
CH3
9 2-Br CH2CH2
CH3
CH3
10 3-Br CH2CH2
CH 3
CH3
11 4-Br CH2CH2
CH3
CH3
12 2,4-Cl2 CH2CH2
CH3
CH3
13 2,6-Cl2 CH2CH2
CH3
CH3
14 3,5-Cl2 CH2CH2
CH3
CH3
15 2,4,6-Cl3
CH2CH2
CH3
CH3
16 2-Cl, 4-CH3
CH2CH2
CH3
CH3
17 2-CH3, 4-Cl
CH2CH2
CH3
CH3
18 2-CH3 CH2CH2
CH3
CH3
19 3-CH3 CH2CH2
CH3
CH3
20 4-CH3 CH2CH2
CH3
CH3
21 4-C2 H5
CH2CH2
CH3
CH3
22 4-i-C3 H7
CH2CH2
CH3
CH3
23 4-t-C4 H9
CH2CH2
CH3
CH3
24 2,4-(CH3)2
CH2CH2
CH3
CH3
25 2,6-(CH3)2
CH2CH2
CH3
CH3
26 2,4,6-(CH3)3
CH2CH2
CH3
CH3
27 2-OCH3, 4-CH3
CH2CH2
CH3
CH3
28 4-OCH3, 2-CH3
CH2CH2
CH3
CH3
29 2-OCH3 CH2CH2
CH3
CH3
30 3-OCH3 CH2CH2
CH3
CH3
31 4-OCH3 CH2CH2
CH3
CH3
32 4-OC2 H5
CH2CH2
CH3
CH3
33 4-O-i-C3 H7
CH2CH2
CH3
CH3
34 2-CF3 CH2CH2
CH3
CH3
35 3-CF3 CH2CH2
CH3
CH3
36 4-CF3 CH2CH2
CH3
CH3
37 2-CN CH2CH2
CH3
CH3
38 4-CN CH2CH2
CH3
CH3
39 3-NO2 CH2CH2
CH3
CH3
40 4-NO2 CH2CH2
CH3
CH3
41 4-C6 H5
CH2CH2
CH3
CH3
42 H CHCH CH3
CH3
Z oil 2960, 1740,
1496, 1455,
1227, 1043,
1017, 962,
760, 692
43 2-F CHCH CH3
CH3
44 3-F CHCH CH3
CH3
45 4-F CHCH CH3
CH3
46 2-Cl, 6-F CHCH CH3
CH3
47 2-Cl CHCH CH3
CH3
48 3-Cl CHCH CH3
CH3
49 4-Cl CHCH CH3
CH3
E/Z oil 2970, 1740,
1492, 1456,
1228, 1091,
1044, 1013,
962, 813
753
50 2-Br CHCH CH3
CH3
51 3-Br CHCH CH3
CH3
52 4-Br CHCH CH3
CH3
53 2,4-Cl2 CHCH CH3
CH3
54 2,6-Cl2 CHCH CH3
CH3
55 3,5-Cl2 CHCH CH3
CH3
56 2,4,6-Cl3
CHCH CH3
CH3
57 2-Cl, 4-CH3
CHCH CH3
CH3
58 2-CH3, 4-Cl
CHCH CH3
CH3
59 2-CH3 CHCH CH3
CH3
60 3-CH3 CHCH CH3
CH3
61 4-CH3 CHCH CH3
CH3
62 3-CH3 CHCH CH3
CH3
63 4-i-C3 H7
CHCH CH3
CH3
64 4-t-C4 H9
CHCH CH3
CH3
65 2,4-(CH3)2
CHCH CH3
CH3
66 2,6-(CH3)2
CHCH CH3
CH3
67 2,4,6-(CH3)3
CHCH CH3
CH3
68 2-OCH3, 4-CH3
CHCH CH3
CH3
69 4-OCH3, 2-CH3
CHCH CH3
CH3
70 2-OCH3 CHCH CH3
CH3
71 3-OCH3 CHCH CH3
CH3
72 4-OCH3 CHCH CH3
CH3
73 4-OC2 H5
CHCH CH3
CH3
74 4-O-iC3 H7
CHCH CH3
CH3
75 2-CF3 CHCH CH3
CH3
76 3-CF3 CHCH CH3
CH3
77 4-CF3 CHCH CH3
CH3
78 2-CN CHCH CH3
CH3
79 4-CN CHCH CH3
CH3
80 3-NO2 CHCH CH3
CH3
81 4-NO2 CHCH CH3
CH3
82 4-C6 H5
CHCH CH3
CH3
83 H CH2 O
CH3
CH3
Z 129-132
2940, 1737
1489, 1455
1343, 1278
1234, 1045
1027, 758
84 2-F CH2 O
CH3
CH3
85 3-F CH2 O
CH3
CH3
E/Z 46-48
2970, 1734,
1592, 1492,
1452, 1278,
1231, 1028,
755
86 4-F CH2 O
CH3
CH3
E/Z 97-99
2970, 1740,
1600, 1513,
1487, 1276,
1224, 1042,
1025, 879,
751
87 2-Cl, 6-F CH2 O
CH3
CH3
88 2-Cl CH2 O
CH3
CH3
89 3-Cl CH2 O
CH3
CH3
E/Z oil 2970, 1742,
1600, 1490,
1453, 1279,
1228, 1044,
1024, 759
90 4-Cl CH2 O
CH3
CH3
Z 106-109
2975, 1738,
1598, 1489,
1277, 1235,
1041, 1026,
873, 759
91 2-Br CH2 O
CH3
CH3
92 3-Br CH2 O
CH3
CH3
93 4-Br CH2 O
CH3
CH3
94 2,4-Cl2 CH2 O
CH3
CH3
95 2,6-Cl2 CH2 O
CH3
CH3
96 3,5-Cl2 CH2 O
CH3
CH3
97 2,4,6-Cl3
CH2 O
CH3
CH3
98 2-CH3, 4-Cl
CH2 O
CH3
CH3
99 2-Cl, 4-CH3
CH2 O
CH3
CH3
100 2-CH3 CH2 O
CH3
CH3
E/Z 2970, 1735,
1489, 1454,
1278, 1231,
1045, 1025,
750
101 3-CH3 CH2 O
CH3
CH3
E/Z 47-49
2970, 1736,
1600, 1490,
1453, 1279,
1227, 1045,
1026, 755
102 4-CH3 CH2 O
CH3
CH3
E/Z 92-94
2970, 1736,
1600, 1490,
1454, 1278,
1232, 1043
1027, 761
103 4-C2 H5
CH2 O
CH3
CH3
104 4-i-C3 H7
CH2 O
CH3
CH3
105 4-t-C4 H9
CH2 O
CH3
CH3
106 2,4-(CH3)2
CH2 O
CH3
CH3
107 2,6-(CH3)2
CH2 O
CH3
CH3
108 2,4,6-(CH3)3
CH2 O
CH3
CH3
109 2-OCH3, 4-CH3
CH2 O
CH3
CH3
110 4-OCH3, 2-CH3
CH2 O
CH3
CH3
111 2-OCH3 CH2 O
CH3
CH3
112 3-OCH3 CH2 O
CH3
CH3
113 4-OCH3 CH2 O
CH3
CH3
114 4-OC2 H5
CH2 O
CH3
CH3
115 4-O-i-C3 H7
CH2 O
CH3
CH3
116 2-CF3 CH2 O
CH3
CH3
117 3-CF3 CH2 O
CH3
CH3
118 4-CF3 CH2 O
CH3
CH3
119 2-CN CH2 O
CH3
CH3
120 4-CN CH2 O
CH3
CH3
121 3-NO2 CH2 O
CH3
CH3
122 4-NO2 CH2 O
CH3
CH3
123 4-C6 H5
CH2 O
CH3
CH3
124 H OCH2
CH3
CH3
E/Z oil 2940, 1742
1598, 1496
1239, 1227
1046, 1019
755
125 2-F OCH2
CH3
CH3
126 2-Cl OCH2
CH3
CH3
127 4-Cl OCH2
CH3
CH3
128 2,4-Cl2 OCH2
CH3
CH3
129 2-CH3, 4-Cl
OCH2
CH3
CH3
130 2-CH3 OCH2
CH3
CH3
131 4-CH3 OCH2
CH3
CH3
132 4-t-C4 H9
OCH2
CH3
CH3
133 2-OCH3 OCH2
CH3
CH3
134 2-CF3 OCH2
CH3
CH3
135 4-NO2 OCH2
CH3
CH3
136 H ethynylene
CH3
CH3
137 2-F ethynylene
CH3
CH3
138 2-Cl ethynylene
CH3
CH3
139 2-Br ethynylene
CH3
CH3
140 4-Br ethynylene
CH3
CH3
141 2-CH3 ethynylene
CH3
CH3
142 4-CH3 ethynylene
CH3
CH3
143 2-OCH3 ethynylene
CH3
CH3
144 4-CF3 ethynylene
CH3
CH3
145 2-NO2 ethynylene
CH3
CH3
146 H CHCH CH3
H
147 H CH2CH2
CH3
H
148 H CHCH CH3
C2 H5
149 H CH2CH2
CH3
C3 H7
150 H CHCH CH3
C3 H7
151 H CH2CH2
CH3
i-C3 H7
152 H CH2CH2
CH3
t-C4 H9
153 H CH2CH2
CH3
C5 H11
154 H CHCH C2 H5
CH3
155 H CH2CH2
C2 H5
CH3
156 H CHCH i-C3 H7
CH3
157 H CH2CH2
i-C3 H7
CH3
158 H CHCH C2 H5
C2 H5
159 H CH2CH2
C2 H5
C2 H5
160 H O CH3
CH3
161 2-F O CH3
CH3
162 2-Cl O CH3
CH3
163 2-Br O CH3
CH3
164 4-Br O CH3
CH3
165 4-Cl O CH3
CH3
166 2-CH3 O CH3
CH3
167 4-CH3 O CH3
CH3
168 2-OCH3 O CH3
CH3
169 4-OCH3 O CH3
CH3
170 4-C6 H5
O CH3
CH3
171 H CHCH H H
172 H CH2CH2
H H
173 4-OCH2C6 H5
CHCH2
CH3
CH3
174 4-OCH2C6 H5
CH2CH2
CH3
CH3
175 4-OC6 H5
CHCH CH3
CH3
176 4-OC6 H 5
CH2CH2
CH3
CH3
177
##STR6## CH2CH2
CH3
CH3
178
##STR7## CH2CH2
CH3
CH3
179
##STR8## CH2CH2
CH3
CH3
180 3-OCH2C6 H5
CH2CH2
CH3
CH3
181
##STR9## CH2CH2
CH3
CH3
182
##STR10## CH2CH2
CH3
CH3
183
##STR11## CH2CH2
CH3
CH3
184
##STR12## CH2CH2
CH3
CH3
185
##STR13## CH2CH2
CH3
CH3
186 3-OC6 H5
CH2CH2
CH3
CH3
187
##STR14## CH2CH2
CH3
CH3
188
##STR15## CH2CH2
CH3
CH3
189
##STR16## CH2CH2
CH3
CH3
190
##STR17## CH2CH2
CH3
CH3
191
##STR18## CH2CH2
CH3
CH3
__________________________________________________________________________

In general terms, the novel compounds are extremely effective on a broad spectrum of phytopathogenic fungi, in particular those from the class consisting of the Ascomycetes, Phycomycetes and Basidiomycetes. Some of them have a systemic action and can be used as foliar and soil fungicides.

The fungicidal compounds are of particular interest for controlling a large number of fungi in various crops or their seeds, especially wheat, rye, barley, oats, rice, Indian corn, cotton, soybeans, coffee, sugar cane, fruit and ornamentals in horticulture and viticulture, and in vegetables such as cucumbers, beans and cucurbits.

The novel compounds are particularly useful for controlling the following plant diseases:

Erysiphe graminis in cereals,

Erysiphe cichoracearum and Sphaerotheca fuliginea in cucurbits,

Podosphaera leucotricha in apples,

Uncinula necator in vines,

Puccinia species in cereals,

Rhizoctonia solani in cotton,

Ustilago species in cereals and sugar cane,

Venturia inaequalis (scab) in apples,

Septoria nodorum in wheat,

Pyrenophora teres in barley,

Botrytis cinerea (gray mold) in strawberries and grapes,

Cercaspora arachidicola in groundnuts,

Pseudocercosporella herpotrichoides in wheat and barley,

Pyricularia oryzae in rice,

Alternaria solani and Phytophthora infestans in potatoes and tomatoes,

Plasmopara viticola in grapes, and

Fusarium and Verticillum species in various plants.

The compounds are applied by spraying or dusting the plants with the active ingredients, or treating the seeds of the plants with the active ingredients. They may be applied before or after infection of the plants or seeds by the fungi.

The novel substances can be converted into conventional formulations such as solutions, emulsions, suspensions, dusts, powders, pastes and granules. The application forms depend entirely on the purposes for which they are intended; they should at all events ensure a fine and uniform distribution of the active ingredient. The formulations are produced in known manner, for example by extending the active ingredient with solvents and/or carriers, with or without the use of emulsifiers and dispersants; if water is used as solvent, it is also possible to employ other organic solvents as auxiliary solvents. Suitable auxiliaries for this purpose are solvents such as aromatics (e.g., xylene, benzene), chlorinated aromatics (e.g., chlorobenzenes), paraffins (e.g., crude oil fractions), alcohols (e.g., methanol, butanol), amines (e.g., ethanolamine, dimethylformamide), and water; carriers such as ground natural minerals (e.g., kaolins, aluminas, talc and chalk) and ground synthetic minerals (e.g., highly disperse silica and silicates); emulsifiers such as nonionic and anionic emulsifiers (e.g., polyoxyethylene fatty alcohol ethers, alkyl sulfonates and aryl sulfonates); and dispersants such as lignin, sulfite waste liquors and methylcellulose.

The fungicides generally contain from 0.1 to 95, and preferably from 0.5 to 90, wt % of active ingredient.

The application rates are from 0.5 to 3 kg or more of active ingredient per hectare, depending on the type of effect desired. The novel compounds may also be used for protecting materials, inter alia for combating wood-destroying fungi such as Coniophora puteana and Pllystictus versicolor. The novel active ingredients may also be used as fungicidal components of oily wood preservatives for protecting wood against wood-discoloring fungi. They are applied by treating, for example impregnating or painting, the wood with them.

The agents and the ready-to-use formulations prepared from them, such as solutions, emulsions, suspensions, powders, dusts, pastes and granules, are applied in conventional manner, for example by spraying, atomizing, dusting, scattering, dressing or watering.

Examples of formulations are given below.

I. 90 parts by weight of compound no. 83 is mixed with 10 parts by weight of N-methyl-alpha-pyrrolidone. A mixture is obtained which is suitable for application in the form of very fine drops.

II. 20 parts by weight of compound no. 124 is dissolved in a mixture consisting of 80 parts by weight of xylene, 10 parts by weight of the adduct of 8 to 10 moles of ethylene oxide and 1 mole of oleic acid-N-monoethanolamide, 5 parts by weight of the calcium salt of dodecylbenzene-sulfonic acid, and 5 parts by weight of the adducts of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

III. 20 parts by weight of compound no. 83 is dissolved in a mixture consisting of 40 parts by weight of cyclohexanone, 30 parts by weight of isobutanol, 20 parts by weight of the adduct of 7 moles of ethylene oxide and 1 mole of isooctylphenol, and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and finely distributing it therein, an aqueous dispersion is obtained.

IV. 20 parts by weight of compound no. 124 is dissolved in a mixture consisting of 25 parts by weight of cyclohexanol, 65 parts by weight of a mineral oil fraction having a boiling point between 210° and 280° C., and 10 parts by weight of the adduct of 40 moles of ethylene oxide and 1 mole of castor oil. By pouring the solution into water and uniformly distributing it therein, an aqueous dispersion is obtained.

V. 80 parts by weight of compound no. 83 is well mixed with 3 arts by weight of the sodium salt of diisobutylnaphthalene-alpha-sulfonic acid, 10 parts by weight of the sodium salt of a lignin-sulfonic acid obtained from a sulfite waste liquor, and 7 parts by weight of powdered silica gel, and triturated in a hammer mill. By uniformly distributing the mixture in water, a spray liquor is obtained.

VI. 3 parts by weight of compound no. 124 is intimately mixed with 97 parts by weight of particulate kaolin. A dust is obtained containing 3% by weight of the active ingredient.

VII. 30 parts by weight of compound no. 83 is intimately mixed with a mixture consisting of 92 parts by weight of powdered silica gel and 8 parts by weight of paraffin oil which has been sprayed onto the surface of this silica gel. A formulation of the active ingredient is obtained having good adherence.

VIII. 40 parts by weight of compound no. 124 is intimately mixed with 10 parts of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate, 2 parts of silica gel and 48 parts of water to give a stable aqueous dispersion. Dilution in water gives an aqueous dispersion.

IX. 20 parts by weight of compound no. 83 is intimately mixed with 2 parts by weight of the calcium salt of dodecylbenzenesulfonic acid, 8 parts by weight of a fatty alcohol polyglycol ether, 2 parts by weight of the sodium salt of a phenolsulfonic acid-urea-formaldehyde condensate and 68 parts by weight of a paraffinic mineral oil. A stable oily dispersion is obtained.

In these application forms, the agents according to the invention may also be present together with other active ingredients, for example herbicides, insecticides, growth regulators, and fungicides, and may furthermore be mixed and applied together with fertilizers. Admixture with other fungicides frequently results in a greater fungicidal action spectrum.

The following list of fungicides with which the novel compounds may be combined is intended to illustrate possible combinations but not to impose any restrictions.

Examples of fungicides which may be combined with the novel compounds are:

sulfur,

dithiocarbamates and their derivatives, such as ferric dimethyldithiocarbamate,

zinc dimethyldithiocarbamate,

zinc ethylenebisdithiocarbamate,

manganese ethylenebisdithiocarbamate,

manganese zinc ethylenediaminebisdithiocarbamate,

tetramethylthiuram disulfides,

ammonia complex of zinc N,N'-ethylenebisdithiocarbamate,

ammonia complex of zinc N,N'-propylenebisdithiocarbamate,

zinc N,N'-propylenebisdithiocarbamate and

N,N'-polypropylenebis (thiocarbamyl) disulfide;

nitro derivatives, such as

dinitro(1-methylheptyl)-phenyl crotonate,

2-sec-butyl-4,6-dinitrophenyl 3,3-dimethylacrylate,

2-sec-butyl-4,6-dinitrophenyl isopropylcarbonate and

diisopropyl 5-nitroisophthalate;

heterocyclic substances, such as

2-heptadecylimidazole-2-yl acetate,

2,4-dichloro-6-(o-chloroanilino)-s-triazine,

O,O-diethyl phthalimidophosphonothioate,

5-amino-1-[-bis-(dimethylamino)-phosphinyl]-3-phenyl-1,2,4-triazole,

2,3-dicyano-1,4-dithiaanthraquinone,

2-thio-1,3-dithio[4,5-b]quinoxaline,

methyl 1-(butylcarbamyl)-2-benzimidazolecarbamate,

2-methoxycarbonylaminobenzimidazole,

2-(fur-2-yl)-benzimidazole,

2-(thiazol-4-yl)benzimidazole,

N-(1,1,2,2-tetrachloroethylthio)-tetrahydrophthalimide,

N-trichloromethylthiotetrahydrophthalimide,

N-trichloromethylthiophthalimide,

N-dichlorofluoromethylthio-N',N'-dimethyl-N-phenylsulfuric acid diamide,

5-ethoxy-3-trichloromethyl-1,2,3-thiadiazole,

2-thiocyanatomethylthiobenzothiazole,

1,4-dichloro-2,5-dimethoxybenzene,

4-(2-chlorophenylhydrazono)-3-methyl-5-isoxazolone,

2-thiopyridine 1-oxide,

8-hydroxyquinoline and its copper salt,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin,

2,3-dihydro-5-carboxanilido-6-methyl-1,4-oxathiin 4,4-dioxide,

2-methyl-5,6-dihydro-5H-pyran-3-carboxanilide,

2-methylfuran-3-carboxanilide,

2,5-dimethylfuran-3-carboxanilide,

2,4,5-trimethylfuran-3-carboxanilide,

2,5-dimethyl-N-cyclohexylfuran-3-carboxamide,

N-cyclohexyl-N-methoxy-2,5-diethylfuran-3-carboxamide,

2-methylbenzanilide,

2-iodobenzanilide,

N-formyl-N-morpholine-2,2,2-trichloroethylacetal, piperazine-1,4-diylbis-(1-(2,2,2-trichloroethyl)-formamide),

1-(3,4-dichloroanilino)-1-formylamino-2,2,2-trichloroethane, 2,6-dimethyl-N-tridecylmorpholine and its salts,

2,6-dimethyl-N-cyclododecylmorpholine and its salts,

N-[3-(p-tert.-butylphenyl)-2-methylpropyl]-cis-2,6-dimethylmorpholine,

N-[3-(p-tert.butylphenyl)-2-methylpropyl]-piperidine,

1-[2-(2,4-dichlorophenyl)-4-ethyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triazole

1-[2-(2,4-dichlorophenyl)-4-n-propyl-1,3-dioxolan-2-ylethyl]-1H-1,2,4-triaz ole,

N-(n-propyl)-N-(2,4,6-trichlorophenoxyethyl)-N'-imidazolyl-urea,

1-(4-chlorophenoxy)3,30367 -dimethyl-1-(1H-1,2,4-triazol-1-yl)-butan-2-one,

1-(4-chlorophenoxy)3,3-dimethyl-1-(1H-1,2,4-triazol-1-yl)butan-2-ol,

α-(2-chlorophenyl)-α-(4-chlorophenyl)-5-pyrimidinemethanol,

5-butyl-(2-dimethylamino-4-hydroxy-6-methylpyrimidine,

bis-(p-chlorophenyl)-3-pyridinemethanol,

1,2-bis-(3-ethoxycarbonyl-2-thioureido)-benzene,

1,2-bis-(3-methoxycarbonyl-2-thioureido)-benzene, and various fungicides, such as

dodecylguanidine acetate,

3-[3-(3,5-dimethyl-2-oxycyclohexyl)-2-hydroxyethyl]glutaramide,

hexachlorobenzene,

DL-methyl-N-(2,6-dimethylphenyl)-N-fur-2-yl alanate,

methyl DL-N-(2,6-dimetehylphenyl)-N-(2'-methoxyacetyl)-alanate,

N-(2,6-dimethylphenyl)-N-chloroacetyl-DL-2-aminobutyrolactone,

methyl DL-N-(2,6-dimethylphenyl)-N-(phenylacetyl)alanate,

5-methyl-5-vinyl-3-(3,5-dichlorophenyl)-2,4-dioxo-1,3-oxazolidine,

3[3,5-dichlorophenyl]-5-methyl-5-methoxymethyl-1,3-oxazolidine-2,4-dione,

3-(3,5-dichlorophenyl)-1-isopropylcarbamylhydantoin,

N-(3,5-dichlorophenyl)-1,2-dimethylcyclopropane-1,2-dicarboximide,

2-cyano-[N-(ethylaminocarbonyl)-2-methoximino]acetamide,

1-[2-(2,4-dichlorophenyl)-pentyl]-1H-1,2,4-triazole,

2,4-difluoro-α-(1H-1,2,4-triazol-1-ylmethyl)-benzhydryl alcohol,

N-(3-chloro-2,6-dinitro-4-trifluoromethylphenyl)-5-trifluoromethyl-3-chloro -2-aminopyridine, and

1-((bis-(4-fluorophenyl)-methylsilyl)-methyl)-1H-1,2,4-triazole.

For the following experiments, the prior art active ingredients N-tridecyl-2,6-dimethylmorpholine (A), its acetate (B) and methyl 2-(4-[p-chlorostyryl]phenyl)-3-methoxyacrylate (C) were used for comparison purposes.

USE EXAMPLE 1

Action on wheat mildew

Leaves of pot-grown wheat seedlings of the "Fruhgold" variety were sprayed with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier, and sprayed, 24 hours after the sprayed-on layer had dried, with spores of wheat mildew (Erysiphe graminis var. tritici). The plants were then set up in the greenhouse at 20° to 22° C. and a relative humidity of 75 to 80%. The extent of mildew spread was assessed after 7 days.

The results of this experiment show that active ingredients nos. 42, 49, 83, 100 and 124, applied as 0.025 and 0.006% (wt %) spray liquors, had a better fungicidal action (90%) than prior art active ingredients A, B and C (70%).

USE EXAMPLE 2

Action on Plasmopara viticola

Leaves of potted vines of the Muller-Thurgau variety were sprayed with aqueous suspensions containing (dry basis) 80% of active ingredient and 20% of emulsifier. To assess the duration of action, the plants were set up, after the sprayed-on layer had dried, for 8 days in the greenhouse. Then the leaves were infected with a zoospore suspension of Plasmopara viticola. The plants were first placed for 16 hours in a water vapor-saturated chamber at 24° C. and then in a greenhouse for 5 days at from 20° to 30° C. To accelerate and intensify the sporangiophore discharge, the plants were then again placed in the moist chamber for 16 hours. The extent of fungus attack was then assessed on the undersides of the leaves.

The results obtained in this experiment show that active ingredients nos. 42, 48, 83, 89, 100 and 124, applied as 0.05% spray liquors, had a good fungicidal action (90%).

USE EXAMPLE 3

Action on Septoria nodorum

Leaves of pot-grown wheat seedlings of the "Jubilar" variety were sprayed to runoff with aqueous liquors containing (dry basis) 80% of active ingredient and 20% of emulsifier. On the following day the plants were infected with an aqueous sport suspension of Septoria nodorum and further cultivated for 7 days at 17° to 19° C. and a relative humidity of 95%. The extent of fungus spread was then assessed visually.

The results obtained show that active ingredients nos. 49, 83 and 124, applied as 0.05% spray liquors, had a good fungicidal action (90%).